CN103255006A - Biodegradable phosphorus-free detergent additive and preparation method thereof - Google Patents
Biodegradable phosphorus-free detergent additive and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a biodegradable phosphorus-free detergent additive and a preparation method thereof. Specifically the biodegradable phosphorus-free detergent additive is a polyaspartic acid grafted copolymer with a side chain containing a glutamic acid group, wherein maleic anhydride and urea are adopted as starting raw materials, reactions such as amination and heat condensation polymerization are performed to produce polysuccinimide, the polysuccinimide and sodium glutamate are subjected to an aminolysis reaction, and then neutralization, cold precipitation, filtration, concentration and drying are performed to obtain the polyaspartic acid grafted copolymer with the side chain containing the glutamic acid group. According to the present invention, the molecular structure of the polyaspartic acid grafted copolymer does not contain phosphorus, and the polyaspartic acid grafted copolymer has characteristics of no toxicity, good biodegradability, good water solubility, good calcium chelation performance and good calcium dispersion performance, and is a highly efficient and environmental-protection synthesis detergent additive.
Description
Technical field
The present invention relates to a kind of biodegradable non-phosphorus washing assistant and preparation method thereof.
Background technology
For a long time, tripoly phosphate sodium STPP is extensive use of in the washing industry as a kind of functional, cheap washing auxiliary detergent always.Yet cause the waters eutrophication owing to phosphorus-containing detergent enters rivers and lakes in a large number, the red tide of occurrence of large-area, havoc ecotope.Therefore since the seventies many countries promulgated in succession that statutory regulations is carried out and prohibited phosphorus, limit phosphorus.Thereby, seek the non-phosphorus builder that inexpensive, nontoxic, functional, environmentally safe can substitute tripoly phosphate sodium STPP simultaneously again, become both at home and abroad in the synthetic detergent exploitation hot fields.
Early stage non-phosphorus washing assistant (yellow soda ash or water glass, low molecule organic carboxylate etc.)---s-generation non-phosphorus washing assistant (4A zeolite, Starso, sodium polyacrylate etc.)---non-phosphorus washing assistant of new generation (modified polyacrylic acid sodium, zeolite P, laminated crystal of sodium disilicate, modified starch, poly aspartic acid, poly-epoxy succinic acid etc.) has been experienced in the development of non-phosphorus washing assistant.In a new generation's non-phosphorus washing assistant, zeolite P is the same with the 4A zeolite poorly soluble, and also because industrial scale is little, price is than 4A zeolite height; Laminated crystal of sodium disilicate is the inorganic non-phosphorus washing assistant that is expected to replace tripoly phosphate sodium STPP, and production cost is to influence its key in application; Modified polyacrylic acid sodium washing auxiliary detergent, what adopt at present is lower-cost maleic anhydride and acrylic acid multipolymer, domestic patent [CN101362811] has been reported the preparation method of this multipolymer, but the biological degradability of polyacrylic acid and acrylic copolymer is poor, is the maximum bottleneck of its widespread use of restriction; At present, the more modified starch washing assistant of research has Sumstar 190 and carboxymethyl starch both at home and abroad, external existing daily use chemicals company uses the modified starch washing assistant in cleaning product, the applied research of domestic modified starch washing assistant also begins, as domestic patent [CN1202133, CN1283666], its shortcoming is that starch is natural high moleculer eompound, exist unstable, easily decompose, dosage is big, foreign matter content is high, performance often has fluctuation, and chelating and dispersing property are not as good as synthetic polymer etc.Poly aspartic acid and poly-epoxy succinic acid, nitrogenous or the oxygen heteroatom of their main chains, have favorable biological degradability, and have certain chelating and dispersing property, can be applicable to washing auxiliary detergent (application [J] of poly aspartic acid in dish washing detergent. the 21st national industrial surface activity agent development seminar, 2008; Domestic patent [CN101514308]).
Poly aspartic acid is the polyamino acid that a kind of side chain has carboxylic acid, has good chelating and dispersing property, and rare biological degradability, can be used as the good substitute of tripoly phosphate sodium STPP.But its chelating and dispersive ability are not as the vinylformic acid-maleic anhydride analog copolymer of present widespread use.For improving the chelating dispersing property of poly aspartic acid, study on the modification to poly aspartic acid had report both at home and abroad, reported as foreign patent [US:6022401] and in the poly aspartic acid molecular structure, to have introduced hydroxyl, phosphonate group etc., and [US:5506335] reported in the poly aspartic acid molecular structure and introduced sulfonic group.
The present invention adopts polysuccinimide and Sodium Glutamate reaction, introduces the L-glutamic acid group in the poly aspartic acid molecular structure, has prepared the modified polyaspartic acid that a kind of side chain has the L-glutamic acid group, has improved calcium chelating, the calcium dispersing property of poly aspartic acid.In addition, the poly aspartic acid graft copolymer that the prepared side chain of the present invention contains the L-glutamic acid group also has favorable biological degradability, is a kind of efficient, environment-friendly type non-phosphorus washing assistant.
Summary of the invention
The purpose of this invention is to provide a kind of biodegradable non-phosphorus washing assistant and preparation method thereof, reduce washing auxiliary detergent to the pollution of environment, reduce the price of washing auxiliary detergent, improve the over-all properties of washing auxiliary detergent.
A kind of biodegradable non-phosphorus washing assistant provided by the invention is the poly aspartic acid graft copolymer that side chain contains the L-glutamic acid group, and its structure is as follows:
In the formula: (a+b)/(a+b+c+d)=0.1 ~ 0.6.
The preparation method of a kind of biodegradable non-phosphorus washing assistant provided by the invention, reaction scheme is as follows:
A kind of biodegradable non-phosphorus washing assistant preparation method of the present invention has following steps:
(1) be starting raw material with maleic anhydride and urea, generate polysuccinimide through amination, thermal polycondensation reaction:
A. add maleic anhydride and distilled water in there-necked flask, the intensification stirring and dissolving to 60 ~ 90 ℃, drips the aqueous solution that contains urea, obtains colourless solution after dropwising, and under 85 ~ 90 ℃, stirring reaction 2 hours obtains settled solution;
B. the settled solution that step a is made obtains white dope 110 ~ 130 ℃ of following underpressure distillation, continues to be warming up to 160 ~ 200 ℃, and under the reduced pressure, condensation reaction 0.5 ~ 1.5 hour obtains solid orange, fragility, is polysuccinimide;
(2) preparation monosodium glutamate solution:
L-glutamic acid is water-soluble, under agitation drip the sodium hydroxide solution of 2mol/L, obtain monosodium glutamate solution, wherein the mol ratio of sodium hydroxide and L-glutamic acid is 1.1 ~ 1.5;
(3) ammonolysis reaction generates the poly aspartic acid graft copolymer aqueous solution that side chain contains the L-glutamic acid group:
The polysuccinimide of above-mentioned steps (1) gained is suspended in water, under agitation slowly drip the monosodium glutamate solution of above-mentioned steps (2) gained, regulating pH with the sodium hydroxide solution of 2mol/L is 8 ~ 10, temperature of reaction is 20 ~ 40 ℃, reaction times is 22 ~ 26 hours, gets the poly aspartic acid graft copolymer aqueous solution that side chain russet contains the L-glutamic acid group.
(4) neutralization, cold analysis, filtration, concentrated, dry:
Above-mentioned steps (3) obtained aqueous solution is regulated pH to 2.8 ~ 3.5 with hydrochloric acid, red tan solution is chilled to 0 ~ 5 ℃ then, after the placement, separate out unreacted L-glutamic acid, filter, filtrate is under less than 100 ℃, moisture is removed in underpressure distillation, and drying obtains brown solid in baking oven then, be the poly aspartic acid graft copolymer that side chain contains the L-glutamic acid group, grind airtight preservation.
In the described step (1), the mol ratio of maleic anhydride and urea is 1.0 ~ 2.0.
In the described step (3), the mol ratio of Sodium Glutamate and polysuccinimide is 0.1 ~ 2.0.
Beneficial effect of the present invention:
Product of the present invention is introduced the L-glutamic acid group at the poly aspartic acid side chain, and its side-chain charges density is increased, and strengthens its chelating dispersing property, and nontoxic, has favorable biological degradability simultaneously.Raw material of the present invention is easy to get, and the preparation method is simple, is convenient to suitability for industrialized production, need not change other processing condition, just adds the L-glutamic acid group in synthetic, and reached the purpose that increases the chelating dispersing property of poly aspartic acid.
Description of drawings:
Fig. 1 side chain contains the infrared spectrum of the poly aspartic acid graft copolymer of L-glutamic acid group.
Fig. 2 side chain contains the poly aspartic acid graft copolymer of L-glutamic acid group
1H NMR spectrogram.
Embodiment
Below in conjunction with example the present invention is done and to describe in further detail.
The testing method of the biodegradability of resulting multipolymer is seen GBT20778-2006 in the following example.
The calcium chelating ability testing method of resulting multipolymer is as follows in the following example:
Accurately weighing 0.15000 ~ 0.2500 g sample is dissolved in it in 250mL volumetric flask with 100mL distilled water, pipettes 25mL CaCl
2Standardized solution (0.05mol/L) is in volumetric flask, and behind the adding distil water constant volume, vibration 30min in gap does filtration with qualitative filter paper.
(1) pipettes above-mentioned filtrate 25mL in the Erlenmeyer flask of 250ml, add 25mL ammonia-chloride buffer solution (pH=10.5) and 4 ~ 5 chromium black T indicators, use the standard solution titration of 0.05mol/L EDTA then, becoming pure blue with solution from burgundy is terminal point.
(2) replicate(determination) is 3 times, averages.
100.08:CaCO
3The mmole quality, mg/mmol;
C
0: CaCl
2The volumetric molar concentration of standardized solution, mol/L;
C
1: the volumetric molar concentration of EDTA standardized solution, mol/L;
V
1: consume the volume of EDTA standardized solution in the titration, mL;
M: sample sample weighting amount, g.
The testing method of resulting multipolymer calcium dispersion force is as follows in the following example:
Be dissolved in the 100mlL deionized water with about l.0000g multipolymer, add 10mL, l0%Na
2CO
3The aqueous solution transfers to 11.0 with the NaOH aqueous solution of 0.5mol/L with the pH value, does not disappear with 0.25mol/L lime acetate aqueous solution titration to muddiness.Calcium carbonate disperses ability mg/g=100.08CV/m.
C: the volumetric molar concentration of calcium acetate solution, mol/L; V: consume the volume of calcium acetate solution during titration, mL; M: sample sample weighting amount, g.
Embodiment 1:
Add 9.8g maleic anhydride and 10mL distilled water in there-necked flask, the intensification stirring and dissolving to 60 ℃, drips the 10mL aqueous solution that contains 3.0g urea, obtains colourless solution after dropwising, and under 85 ~ 90 ℃, stirs 2 hours, obtains settled solution; The above-mentioned settled solution that makes 130 ℃ of following underpressure distillation, is obtained the mixture of white crystal and a small amount of thickness, continue to be warming up to 180 ℃, under the reduced pressure, condensation reaction 0.5 hour obtains solid orange, fragility, is polysuccinimide; With the sodium hydroxide solution dissolving of 1.47g L-glutamic acid with the 2mol/L of 6.5mL, obtain monosodium glutamate solution; In the there-necked flask of being furnished with stirring, thermometer, dropping funnel, add the 4.85g polysuccinimide, add 15mL water again, it is suspended in water, under agitation slowly drip monosodium glutamate solution, and to regulate pH with the sodium hydroxide solution of 2mol/L be 8, temperature of reaction is 30 ℃, and the reaction times is 24 hours, gets the poly aspartic acid graft copolymer solution that side chain russet contains the L-glutamic acid group.Regulate pH to 2.8 ~ 3.5 with hydrochloric acid, red tan solution is chilled to 0 ~ 5 ℃, separate out unreacted L-glutamic acid, filter, filtrate under less than 100 ℃, underpressure distillation, remove moisture, drying obtains brown solid in baking oven then, and namely side chain contains the poly aspartic acid graft copolymer of L-glutamic acid group, grinds airtight preservation.The calcium chelating value of the polymkeric substance of embodiment 1 is: 199.8mg CaCO
3/ g; The calcium dispersion force is: 100.8mg CaCO
3/ g; 28 days biological degradation rate reaches: 66%.
Embodiment 2:
Add 10.0g maleic anhydride and 12mL distilled water in there-necked flask, the intensification stirring and dissolving to 70 ℃, drips the 10mL aqueous solution that contains 3.6g urea, obtains colourless solution after dropwising, and under 85 ~ 90 ℃, stirs 2 hours, obtains settled solution; The above-mentioned settled solution that makes 120 ℃ of following underpressure distillation, is obtained the mixture of white crystal and a small amount of thickness, continue to be warming up to 160 ℃, under the reduced pressure, condensation reaction reaction 1.0 hours obtains solid orange, fragility, is polysuccinimide; With the sodium hydroxide solution dissolving of 4.41g L-glutamic acid with the 2mol/L of 16.5mL, obtain monosodium glutamate solution; In the there-necked flask of being furnished with stirring, thermometer, dropping funnel, add the 4.85g polysuccinimide, add 15mL water again, it is suspended in water, under agitation slowly drip monosodium glutamate solution, and to regulate pH with the sodium hydroxide solution of 2mol/L be 8, temperature of reaction is 30 ℃, and the reaction times is 24 hours, gets the poly aspartic acid graft copolymer solution that side chain russet contains the L-glutamic acid group.Regulate pH to 2.8 ~ 3.5 with hydrochloric acid, red tan solution is chilled to 0 ~ 5 ℃, separate out unreacted L-glutamic acid, filter, filtrate under less than 100 ℃, underpressure distillation, remove moisture, drying obtains brown solid in baking oven then, and namely side chain contains the poly aspartic acid graft copolymer of L-glutamic acid group, grinds airtight preservation.The calcium chelating value of the polymkeric substance of embodiment 2 is: 202.0mg CaCO
3/ g; The calcium dispersion force is: 105.8mg CaCO
3/ g; 28 days biological degradation rate reaches: 65%.
Embodiment 3:
Add 9.8g maleic anhydride and 12mL distilled water in there-necked flask, the intensification stirring and dissolving to 80 ℃, drips the 10mL aqueous solution that contains 4.2g urea, obtains colourless solution after dropwising, and under 85 ~ 90 ℃, stirs 2 hours, obtains settled solution; The above-mentioned settled solution that makes 110 ℃ of following underpressure distillation, is obtained the mixture of white crystal and a small amount of thickness, continue to be warming up to 200 ℃, under the reduced pressure, condensation reaction reaction 1.0 hours obtains solid orange, fragility, is polysuccinimide; With the sodium hydroxide solution dissolving of 7.35g L-glutamic acid with the 2mol/L of 37.5mL, obtain monosodium glutamate solution; In the there-necked flask of being furnished with stirring, thermometer, dropping funnel, add the 4.85g polysuccinimide, add 15mL water again, it is suspended in water, under agitation slowly drip monosodium glutamate solution, and to regulate pH with the sodium hydroxide solution of 2mol/L be 9, temperature of reaction is 30 ℃, and the reaction times is 24 hours, gets the poly aspartic acid graft copolymer solution that side chain russet contains the L-glutamic acid group.Regulate pH to 2.8 ~ 3.5 with hydrochloric acid, red tan solution is chilled to 0 ~ 5 ℃, separate out unreacted L-glutamic acid, filter, filtrate under less than 100 ℃, underpressure distillation, remove moisture, drying obtains brown solid in baking oven then, and namely side chain contains the poly aspartic acid graft copolymer of L-glutamic acid group, grinds airtight preservation.The calcium chelating value of the polymkeric substance of embodiment 3 is: 210.5mg CaCO
3/ g; The calcium dispersion force is: 108.8mg CaCO
3/ g; 28 days biological degradation rate reaches: 64%.
Embodiment 4:
Add 9.8g maleic anhydride and 15mL distilled water in there-necked flask, the intensification stirring and dissolving to 90 ℃, drips the 10mL aqueous solution that contains 4.8g urea, obtains colourless solution after dropwising, and under 85 ~ 90 ℃, stirs 2 hours, obtains settled solution; The above-mentioned settled solution that makes 130 ℃ of following underpressure distillation, is obtained the mixture of white crystal and a small amount of thickness, continue to be warming up to 180 ℃, under the reduced pressure, condensation reaction reaction 1.5 hours obtains solid orange, fragility, is polysuccinimide; With the sodium hydroxide solution dissolving of 8.82g L-glutamic acid with the 2mol/L of 39.0mL, obtain monosodium glutamate solution; In the there-necked flask of being furnished with stirring, thermometer, dropping funnel, add the 4.85g polysuccinimide, add 15mL water again, it is suspended in water, under agitation slowly drip monosodium glutamate solution, and to regulate pH with the sodium hydroxide solution of 2mol/L be 9, temperature of reaction is 30 ℃, and the reaction times is 24 hours, gets the poly aspartic acid graft copolymer solution that side chain russet contains the L-glutamic acid group.Regulate pH to 2.8 ~ 3.5 with hydrochloric acid, red tan solution is chilled to 0 ~ 5 ℃, separate out unreacted L-glutamic acid, filter, filtrate under less than 100 ℃, underpressure distillation, remove moisture, and then drying obtains brown solid in the baking oven, and namely side chain contains the poly aspartic acid graft copolymer of L-glutamic acid group, grinds airtight preservation.The calcium chelating value of the polymkeric substance of embodiment 4 is: 233.2mg CaCO
3/ g; CaCO
3Dispersion force is: 108.9mg CaCO
3/ g; 28 days biological degradation rate reaches: 63%.
Embodiment 5:
Add 9.8g maleic anhydride and 15mL distilled water in there-necked flask, the intensification stirring and dissolving to 80 ℃, drips the 10mL aqueous solution that contains 5.4g urea, obtains colourless solution after dropwising, and under 85 ~ 90 ℃, stirs 2 hours, obtains settled solution; The above-mentioned settled solution that makes 120 ℃ of following underpressure distillation, is obtained the mixture of white crystal and a small amount of thickness, continue to be warming up to 160 ℃, under the reduced pressure, condensation reaction reaction 1.5 hours obtains solid orange, fragility, is polysuccinimide; With the sodium hydroxide solution dissolving of 11.76g L-glutamic acid with the 2mol/L of 44.0mL, obtain monosodium glutamate solution; In the there-necked flask of being furnished with stirring, thermometer, dropping funnel, add the 4.85g polysuccinimide, add 15mL water again, it is suspended in water, under agitation slowly drip monosodium glutamate solution, and to regulate pH with the sodium hydroxide solution of 2mol/L be 10, temperature of reaction is 30 ℃, and the reaction times is 24 hours, gets the poly aspartic acid graft copolymer solution that side chain russet contains the L-glutamic acid group.Regulate pH to 2.8 ~ 3.5 with hydrochloric acid, red tan solution is chilled to 0 ~ 5 ℃, separate out unreacted L-glutamic acid, filter, filtrate under less than 100 ℃, underpressure distillation, remove moisture, and then drying obtains brown solid in the baking oven, and namely side chain contains the poly aspartic acid graft copolymer of L-glutamic acid group, grinds airtight preservation.The calcium chelating value of the polymkeric substance of embodiment 5 is: 215.3mg CaCO
3/ g; The calcium dispersion force is: 107.2mg CaCO
3/ g; 28 days biological degradation rate reaches: 63%.
Embodiment 6:
Add 9.8g maleic anhydride and 15mL distilled water in there-necked flask, the intensification stirring and dissolving to 70 ℃, drips the 10mL aqueous solution that contains 6.0g urea, obtains colourless solution after dropwising, and under 85 ~ 90 ℃, stirs 2 hours, obtains settled solution; The above-mentioned settled solution that makes 110 ℃ of following underpressure distillation, is obtained the mixture of white crystal and a small amount of thickness, continue to be warming up to 200 ℃, under the reduced pressure, condensation reaction reaction 1.0 hours obtains solid orange, fragility, is polysuccinimide; With the sodium hydroxide solution dissolving of 14.7g L-glutamic acid with the 2mol/L of 55.0mL, obtain monosodium glutamate solution; In the there-necked flask of being furnished with stirring, thermometer, dropping funnel, add the 4.85g polysuccinimide, add 15mL water again, it is suspended in water, under agitation slowly drip monosodium glutamate solution, and to regulate pH with the sodium hydroxide solution of 2mol/L be 10, temperature of reaction is 20 ℃, and the reaction times is 26 hours, gets the poly aspartic acid graft copolymer solution that side chain russet contains the L-glutamic acid group.Regulate pH to 2.8 ~ 3.5 with hydrochloric acid, red tan solution is chilled to 0 ~ 5 ℃, separate out unreacted L-glutamic acid, filter, filtrate under less than 100 ℃, underpressure distillation, remove moisture, and then drying obtains brown solid in the baking oven, and namely side chain contains the poly aspartic acid graft copolymer of L-glutamic acid group, grinds airtight preservation.The calcium chelating value of the polymkeric substance of embodiment 6 is: 207.7mg CaCO
3/ g; The calcium dispersion force is: 102.7mg CaCO
3/ g; 28 days biological degradation rate reaches: 62%.
Claims (4)
1. a biodegradable non-phosphorus washing assistant is characterized in that described biodegradable non-phosphorus washing assistant is the poly aspartic acid graft copolymer that side chain contains the L-glutamic acid group, and its structure is as follows:
In the formula: (a+b)/(a+b+c+d)=0.1 ~ 0.6.
2. the preparation method of the described biodegradable non-phosphorus washing assistant of claim 1 is characterized in that having following steps:
(1) be starting raw material with maleic anhydride and urea, generate polysuccinimide through amination, thermal polycondensation reaction:
A. add maleic anhydride and distilled water in there-necked flask, the intensification stirring and dissolving to 60 ~ 90 ℃, drips the aqueous solution that contains urea, obtains colourless solution after dropwising, and under 85 ~ 90 ℃, stirring reaction 2 hours obtains settled solution;
B. the settled solution that step a is made obtains white dope 110 ~ 130 ℃ of following underpressure distillation, continues to be warming up to 160 ~ 200 ℃, and under the reduced pressure, condensation reaction 0.5 ~ 1.5 hour obtains solid orange, fragility, is polysuccinimide;
(2) preparation monosodium glutamate solution:
L-glutamic acid is water-soluble, under agitation drip the sodium hydroxide solution of 2mol/L, obtain monosodium glutamate solution, wherein the mol ratio of sodium hydroxide and L-glutamic acid is 1.1 ~ 1.5;
(3) ammonolysis reaction generates the poly aspartic acid graft copolymer aqueous solution that side chain contains the L-glutamic acid group:
The polysuccinimide of above-mentioned steps (1) gained is suspended in water, under agitation slowly drip the monosodium glutamate solution of above-mentioned steps (2) gained, regulating pH with the sodium hydroxide solution of 2mol/L is 8 ~ 10, temperature of reaction is 20 ~ 40 ℃, reaction times is 22 ~ 26 hours, gets the poly aspartic acid graft copolymer aqueous solution that side chain russet contains the L-glutamic acid group;
(4) neutralization, cold analysis, filtration, concentrated, dry:
Above-mentioned steps (3) obtained aqueous solution is regulated pH to 2.8 ~ 3.5 with hydrochloric acid, red tan solution is chilled to 0 ~ 5 ℃ then, after the placement, separate out unreacted L-glutamic acid, filter, filtrate is under less than 100 ℃, underpressure distillation, remove moisture, drying obtains brown solid in baking oven then, and namely side chain contains the poly aspartic acid graft copolymer of L-glutamic acid group.
3. preparation method according to claim 2, it is characterized in that: in the described step (1), the mol ratio of maleic anhydride and urea is 1.0 ~ 2.0.
4. preparation method according to claim 2, it is characterized in that: in the described step (3), the mol ratio of Sodium Glutamate and polysuccinimide is 0.1 ~ 2.0.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530428A (en) * | 2014-12-22 | 2015-04-22 | 安徽大学 | Preparation method of modified polyaspartic acid copolymer |
| CN105482117A (en) * | 2016-01-19 | 2016-04-13 | 北京理工大学 | Polyaspartic acid/urea graft copolymer as well as preparation method and application thereof |
| CN111020609A (en) * | 2019-12-30 | 2020-04-17 | 江苏智泰新能源科技有限公司 | Preparation method of cleaning preservative |
-
2013
- 2013-02-02 CN CN201310040392.XA patent/CN103255006B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| ZHANG YULING ET AL: "Microwave-assisted Synthesis of Modified Polyaspartic Acid in Solvent", 《CHIN.J.CHEM.ENG》 * |
| 孟飞: "合成洗涤剂代磷助剂的发展与应用", 《滁州职业技术学院学报》 * |
| 许智芳等: "代磷洗涤助剂的性能及应用前景", 《中国洗涤用品工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530428A (en) * | 2014-12-22 | 2015-04-22 | 安徽大学 | Preparation method of modified polyaspartic acid copolymer |
| CN105482117A (en) * | 2016-01-19 | 2016-04-13 | 北京理工大学 | Polyaspartic acid/urea graft copolymer as well as preparation method and application thereof |
| CN105482117B (en) * | 2016-01-19 | 2017-09-29 | 北京理工大学 | Poly-aspartate/urea graft copolymer and its preparation method and application |
| CN111020609A (en) * | 2019-12-30 | 2020-04-17 | 江苏智泰新能源科技有限公司 | Preparation method of cleaning preservative |
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